PL195428B1 - Use of polyacids to treat mineral fertilizers containing a nitrification inhibitor - Google Patents

Use of polyacids to treat mineral fertilizers containing a nitrification inhibitor

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Publication number
PL195428B1
PL195428B1 PL97361333A PL36133397A PL195428B1 PL 195428 B1 PL195428 B1 PL 195428B1 PL 97361333 A PL97361333 A PL 97361333A PL 36133397 A PL36133397 A PL 36133397A PL 195428 B1 PL195428 B1 PL 195428B1
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PL
Poland
Prior art keywords
dimethylpyrazole
chloro
methylpyrazole
hydroxymethyl
fertilizer
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PL97361333A
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Polish (pl)
Inventor
Thomas Barth
Norbert Rieber
Randall Evan Gold
Jürgen Dressel
Klaus Erhardt
Von Locquengh Klaus Horchler
Edgar Leibold
Stefan Rittinger
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Basf Ag
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Publication of PL195428B1 publication Critical patent/PL195428B1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
    • C05F3/00—Fertilisers from human or animal excrements, e.g. manure
    • C—CHEMISTRY; METALLURGY
    • C05—FERTILISERS; MANUFACTURE THEREOF
    • C05G—MIXTURES OF FERTILISERS COVERED INDIVIDUALLY BY DIFFERENT SUBCLASSES OF CLASS C05; MIXTURES OF ONE OR MORE FERTILISERS WITH MATERIALS NOT HAVING A SPECIFIC FERTILISING ACTIVITY, e.g. PESTICIDES, SOIL-CONDITIONERS, WETTING AGENTS; FERTILISERS CHARACTERISED BY THEIR FORM
    • C05G3/00—Mixtures of one or more fertilisers with additives not having a specially fertilising activity
    • C05G3/90—Mixtures of one or more fertilisers with additives not having a specially fertilising activity for affecting the nitrification of ammonium compounds or urea in the soil
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
    • Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/141—Feedstock
    • Y02P20/145—Feedstock the feedstock being materials of biological origin
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
    • Y02P60/20—Reduction of greenhouse gas [GHG] emissions in agriculture, e.g. CO2
    • Y02P60/21—Dinitrogen oxide [N2O], e.g. using aquaponics, hydroponics or efficiency measures
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S71/00—Chemistry: fertilizers
    • Y10S71/902—Nitrification inhibition

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Soil Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Fertilizers (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The use of inorganic or organic poly acids is claimed for treating mineral fertilisers containing a nitrification inhibitor. The use of compounds of formula (I) is claimed as nitrification inhibitors. R1 = H, halo or 1-4C alkyl; R2 = 1-4C alkyl; R3 = H or CH2OH, and when R3 = H, the compound may be converted to a phosphoric acid salt. A mineral fertiliser containing a poly acid and optionally (I) is also claimed. 3,4-dimethylpyrazole (Ia), 4-chloro-3-methyl-pyrazole (Ib), N-hydroxymethyl-3,4-dimethylpyrazole (Ic), N-hydroxymethyl-4-chloro-3-methylpyrazole (Id), acid addition salts of (Ic) and (Id), and mixtures of two or more of (Ia)-(d) are new.

Description

Opis wynalazkuDescription of the invention

Przedmiotem wynalazku są nowe pochodne pirazolowe, ich zastosowanie jako inhibitorów nitryfikacji oraz nawozy mineralne zawierające azot i nowe pochodne pirazolowe. W celu dostarczania w rolnictwie roślinom potrzebnego im azotu, stosuje się głównie związki amonowe jako nawóz. Związki amonowe w glebie we względnie krótkim czasie ulegają mikrobiologicznej przemianie do azotanu (nitryfikacja). Jednakże azotan może być wymywany z gleby, w wyniku czego zmniejsza się ilość składnika pokarmowego dla roślin tak, że z tego względu niepożądana jest szybka nitryfikacja. Dlatego w celu lepszego wykorzystania nawozu dodaje się do niego inhibitory nitryfikacji. Znaną grupę inhibitorów nitryfikacji stanowią związki pirazolowe.The subject of the invention are new pyrazole derivatives, their use as nitrification inhibitors and nitrogen-containing mineral fertilizers and new pyrazole derivatives. In order to provide plants with the nitrogen they need in agriculture, mainly ammonium compounds are used as fertilizer. Ammonium compounds in the soil undergo microbial transformation into nitrate (nitrification) in a relatively short time. However, nitrate may be leached from the soil, thereby reducing the amount of plant nutrient, so that rapid nitrification is therefore undesirable. Therefore, in order to make better use of the fertilizer, nitrification inhibitors are added to it. A known group of nitrification inhibitors are the pyrazole compounds.

W przypadku stosowania związków pirazolowych jako inhibitory nitryfikacji problemem jest ich duża lotność. A zatem przy składowaniu preparatów nawozowych zawierających związki pirazolowe następuje ciągły ubytek substancji czynnej na skutek odparowania. Z tego względu związki pirazolowe w wyniku odpowiednich zabiegów muszą być preparowane w nielotnej postaci. W celu utrwalenia związków pirazolowych przeprowadzano je na przykład w kompleksy z metalami przejściowymi, jak kompleksy z cynkiem, co przedstawiono na przykład w opisie patentowym US 4 522 642. Przez to można obniżyć lotność substancji czynnych. Jednak z uwagi na ochronę środowiska niepożądane jest nanoszenie cynku, miedzi albo manganu na duże powierzchnie gleby. Kompleksy z metalami alkalicznymi albo metalami ziem alkalicznych są tolerowane przez środowisko, ale są one niewystarczająco trwałe i ulegają hydrolizie w wodnym otoczeniu.A problem with the use of pyrazole compounds as nitrification inhibitors is their high volatility. Thus, during the storage of fertilizer formulations containing pyrazole compounds, there is a continuous loss of active ingredient due to evaporation. For this reason, pyrazole compounds must be prepared in a non-volatile form as a result of appropriate treatments. In order to fix the pyrazole compounds, they have been converted, for example, into complexes with transition metals, such as complexes with zinc, as is shown, for example, in US Pat. No. 4,522,642. As a result, the volatility of the active compounds can be lowered. However, for environmental reasons, it is undesirable to apply zinc, copper or manganese over large soil surfaces. Complexes with alkali metals or alkaline earth metals are environmentally tolerable, but are insufficiently stable and hydrolyze in the aqueous environment.

Ponadto próbowano zmniejszyć lotność związków pirazolowych przez zobojętnienie ich mineralnymi kwasami, jak kwasem fosforowym albo solnym. W opisie patentowym DE-A-4 128 828 omówiono stosowanie azotanów i fosforanów 3-metylopirazolu do pokrywania nawozów. W opisie patentowym US 3 635 690 przedstawiono również stabilizację pochodnych pirazolu za pomocą mineralnych kwasów, jak kwasu solnego, siarkowego, azotowego i fosforowego. Te kwasowe sole związków pirazolowych są jednak jeszcze skłonne do hydrolizy i z tego względu nie do wszystkich zastosowań nadają się.In addition, attempts have been made to reduce the volatility of pyrazole compounds by neutralizing them with mineral acids such as phosphoric or hydrochloric acid. DE-A-4 128 828 describes the use of 3-methylpyrazole nitrates and phosphates for coating fertilizers. U.S. Patent 3,635,690 also describes the stabilization of pyrazole derivatives with mineral acids such as hydrochloric, sulfuric, nitric and phosphoric acids. These acid salts of the pyrazole compounds are, however, still prone to hydrolysis and are therefore not suitable for all applications.

Dalej w opisie patentowym DE-A-4 128 828 omówiono powlekanie pokrytego nawozu woskiem albo olejem. Jednak sposób ten w przypadku higroskopijnych soli substancji czynnych nie prowadzi do zadowalającej odporności na hydrolizę.Further, DE-A-4 128 828 describes the coating of a coated fertilizer with wax or oil. However, this method does not lead to a satisfactory resistance to hydrolysis in the case of hygroscopic active compound salts.

Poza tym stosowano preparaty pirazoli z polimerycznymi substancjami pomocniczymi. I tak w opisie patentowym DD 260 486 przedstawiono preparaty pirazoli w kondensatach mocznik-formaldehyd. Wbudowanie substancji czynnych w matrycę polimerową hamuje jednak ruchliwość ich w glebie. Z tego względu w przypadku tej formy użytkowej subtelnie rozdrobniony preparat i nawóz muszą być dokładnie wymieszane z glebą przeznaczoną do nawożenia. W przeciwnym razie inhibitor nitryfikacji z matrycą polimerową pozostanie na powierzchni gleby. Jednak konieczność wymieszania preparatu, nawozu i gleby jest nakładochłonna.In addition, pyrazole preparations with polymeric auxiliaries were used. Thus, the patent DD 260 486 describes pyrazole preparations in urea-formaldehyde condensates. The incorporation of active substances into the polymer matrix, however, inhibits their mobility in the soil. For this reason, in this formulation, the finely divided preparation and fertilizer must be thoroughly mixed with the soil to be fertilized. Otherwise, the polymer matrix nitrification inhibitor will remain on the soil surface. However, the necessity to mix the preparation, fertilizer and soil is time consuming.

Zadaniem omawianego wynalazku było opracowanie nawozów mineralnych, które zawierają inhibitor nitryfikacji, którego zawartość podczas składowania i nanoszenia nawozu zmienia się nieznacznie, który po naniesieniu nawozu pozostaje obficie w glebie i może rozwijać tam swoje działanie. Ponadto należało opracować nowe inhibitory nitryfikacji.The task of the present invention was to develop mineral fertilizers which contain a nitrification inhibitor whose content changes slightly during storage and application of the fertilizer, which remains abundantly in the soil after the fertilizer is applied and can develop its action there. In addition, new nitrification inhibitors needed to be developed.

Przedmiotem wynalazku są zatem nowe pochodne pirazolowe: N-hydroksymetylo-4-chloro-3-metylopirazol, N-hydroksymetylo-3,4-dimetylopirazol, sól addycyjna 3,4-dimetylopirazolu z kwasem fosforowym, sól addycyjna 4-chloro-3-metylopirazolu z kwasem fosforowym, oraz zastosowanie pochodnych pirazolowych: N-hydroksymetylo-4-chloro-3-metylopirazolu, N-hydroksymetylo-3,4-dimetylopirazolu, soli addycyjnej 3,4-dimetylopirazolu z kwasem fosforowym, soli addycyjnej 4-chloro-3-metylopirazolu z kwasem fosforowym, chlorowodorku 3,4-dimetylopirazolu, jako inhibitorów nitryfikacji.The subject of the invention is therefore new pyrazole derivatives: N-hydroxymethyl-4-chloro-3-methylpyrazole, N-hydroxymethyl-3,4-dimethylpyrazole, 3,4-dimethylpyrazole addition salt with phosphoric acid, 4-chloro-3-methylpyrazole addition salt with phosphoric acid, and the use of pyrazole derivatives: N-hydroxymethyl-4-chloro-3-methylpyrazole, N-hydroxymethyl-3,4-dimethylpyrazole, 3,4-dimethylpyrazole addition salt with phosphoric acid, 4-chloro-3- addition salt methylpyrazole with phosphoric acid, 3,4-dimethylpyrazole hydrochloride as nitrification inhibitors.

Przedmiotem wynalazku są również nawozy mineralne zawierające azot i zawierające te wyżej wymienione inhibitory, których zawartość podczas składowania i nanoszenia nawozu zmienia się nieznacznie, które po naniesieniu nawozu pozostają obficie w glebie i mogą rozwijać tam swoje działanie. Nawóz mineralny według wynalazku zawierający azot i wyżej wymienione inhibitory nitryfikacji zawiera co najmniej jeden wyżej wymieniony związek pirazolowy w ilości 0,01 do 1,5% wagowych.The invention also relates to nitrogen-containing mineral fertilizers containing the above-mentioned inhibitors, the content of which changes slightly during storage and application of the fertilizer, which remain abundantly in the soil after fertilization and can develop their effect there. The nitrogen-containing mineral fertilizer according to the invention and the above-mentioned nitrification inhibitors contain at least one of the above-mentioned pyrazole compounds in an amount of 0.01 to 1.5% by weight.

Nawóz mineralny zawiera inhibitor nitryfikacji, który występuje w nawozie mineralnym albo na jego powierzchni.Mineral fertilizer contains a nitrification inhibitor that is present in or on the surface of the mineral fertilizer.

Nawozy mineralne nanosi się na rolę w postaci proszku lub granulatu.Mineral fertilizers are applied to the soil in the form of powder or granules.

PL 195 428 B1PL 195 428 B1

W zgodnych z wynalazkiem nawozach mineralnych zawierających azot stosuje się wyżej opisane związki pirazolowe.The above-described pyrazole compounds are used in the nitrogen-containing mineral fertilizers according to the invention.

Związki pirazolowe według wynalazku można stosować w postaci zasadowej, jak również w postaci soli addycyjnych z mineralnymi kwasami takimi jak kwas solny i fosforowy, korzystnie kwas fosforowy.The pyrazole compounds of the invention can be used in basic form as well as in addition salts with mineral acids such as hydrochloric and phosphoric acid, preferably phosphoric acid.

Przykładami odpowiednich soli są więc chlorowodorki i sole addycyjne z kwasem fosforowym.Examples of suitable salts are therefore the hydrochlorides and the phosphoric acid addition salts.

W wyniku zastosowania soli addycyjnych związków pirozolowych z kwasami można dalej obniżyć lotność związków.By using acid addition salts of the pyrosol compounds, the volatility of the compounds can be further reduced.

Zatem według wynalazku stosuje się korzystnie sole addycyjne związków pirazolowych z kwasami w kombinacji z traktowaniem nimi nawozu.According to the invention, therefore, the acid addition salts of the pyrazole compounds are preferably used in combination with the treatment of a fertilizer.

Ogólnie wytwarzanie różnych związków pirazolowych jest znane i przedstawione na przykład w opisach patentowych EP-A-0 474 037, DE-A 3 840 342 i EP-A-0 467 707.In general, the preparation of various pyrazole compounds is known and is described, for example, in EP-A-0 474 037, DE-A 3 840 342 and EP-A-0 467 707.

W celu wytworzenia N-hydroksypirazoli odpowiednie pirazole poddaje się reakcji w metanolu z formaliną. Potem odparowuje się nadmiar rozpuszczalnika, przy czym otrzymuje się związki w postaci stałej substancji. Odnośnie wytwarzania 3,4-dimetylopirazolu można wskazać na pracę Noyce'a i współpracowników, Jour. of Org. Chem. 20, 1955, 1681 - 1682.To prepare the N-hydroxypyrazoles, the corresponding pyrazoles are reacted in methanol with formalin. The excess solvent was then evaporated to give the compounds as a solid. Regarding the production of 3,4-dimethylpyrazole, reference can be made to the work of Noyce et al., Jour. of Org. Chem. 20, 1955, 1681-1682.

Sole addycyjne związków pirazolowych z kwasami otrzymuje się w wyniku reakcji pirazoli z równoważnikiem odpowiedniego kwasu. Wytwarzanie chlorowodorku 4-chloro-3-metylo-pirazolu opisano w pracy Hijttel'a i współpracowników, Liebigs Anm. Chem. 1956, 598, 186, 194.Acid addition salts of pyrazole compounds are obtained by reacting pyrazoles with an equivalent of the appropriate acid. The preparation of 4-chloro-3-methyl-pyrazole hydrochloride is described in Hijttel et al., Liebigs Anm. Chem. 1956, 598, 186, 194.

Zgodne z wynalazkiem są nawozy mineralne zawierające azot. Są to nawozy zawierające amon albo mocznik. Przykładami tego rodzaju nawozów mineralnych zawierających amon są nawóz NPK, saletra wapniowo-amonowa, mieszanina saletry amonowej i siarczanu amonowego, siarczan amonowy albo fosforan amonowy.The invention relates to nitrogen-containing mineral fertilizers. These are fertilizers containing ammonium or urea. Examples of this type of ammonium-containing mineral fertilizer are NPK fertilizer, calcium ammonium nitrate, a mixture of ammonium nitrate and ammonium sulphate, ammonium sulphate or ammonium phosphate.

Nawozy mineralne mogą występować w postaci proszku albo granulatu.Mineral fertilizers can be in the form of powder or granules.

Nawóz mineralny zawiera 0,01 do 1 ,5% wagowego inhibitora nitryfikacji w odniesieniu do traktowanego nawozu mineralnego.The mineral fertilizer contains 0.01 to 1.5% by weight of the nitrification inhibitor, based on the treated mineral fertilizer.

Nawóz nieorganiczny traktowany inhibitorem według wynalazku zawiera co najmniej jeden inhibitor nitryfikacji.The inhibitor-treated inorganic fertilizer according to the invention comprises at least one nitrification inhibitor.

Inhibitor nitryfikacji może występować w mieszaninie z nawozem mineralnym albo można go nanieść na nawóz mineralny.The nitrification inhibitor may be present in a mixture with the mineral fertilizer or it may be applied to the mineral fertilizer.

Nieorganiczne nawozy zawierają związki pirazolowe lub ich sole z kwasami. Korzystnie nieorganiczne nawozy są traktowane kwasem poli(met)akrylowym lub kwasem polifosforowym.Inorganic fertilizers contain pyrazole compounds or their salts with acids. Preferably, the inorganic fertilizers are treated with poly (meth) acrylic acid or polyphosphoric acid.

Opisanych inhibitorów nitryfikacji albo nawozów mineralnych według jednej z postaci wykonania wynalazku nie stosuje się do traktowania gleb, które przewidziane są do upraw kukurydzy, bawełny, pszenicy, ryżu, jęczmienia i/albo buraków cukrowych, albo odpowiednich upraw. Pochodne pirazolowe można stosować do stabilizacji gnojowicy albo ciekłych preparatów nawozowych, jak roztworów azotan amonowy-mocznik albo ciekłego amoniaku.The described nitrification inhibitors or mineral fertilizers according to one embodiment of the invention are not applicable to the treatment of soils which are intended for the cultivation of corn, cotton, wheat, rice, barley and / or sugar beet or suitable crops. The pyrazole derivatives can be used to stabilize slurry or liquid fertilizer formulations, such as ammonium nitrate-urea solutions or liquid ammonia.

Wynalazek opisano bliżej za pomocą przykładów.The invention is described in more detail by means of examples.

PrzykładyExamples

Wytwarzanie N-hydroksymetylo-3,4-dimetylopirazolu 96 g (1,0 mol) 3,4-dimetylopirazolu w 50 ml metanolu rozpuszczono w 100 g (1,0 mol) 30%formaliny, w temperaturze pokojowej. Następnie odparowano wodę i metanol. Tytułowy związek pozostał w postaci białej substancji stałej. Wydajność 95%.Preparation of N-Hydroxymethyl-3,4-dimethylpyrazole 96 g (1.0 mol) of 3,4-dimethylpyrazole in 50 ml of methanol were dissolved in 100 g (1.0 mol) of 30% formalin at room temperature. Then water and methanol were evaporated. The title compound remained as a white solid. 95% yield.

Wytwarzanie N-hydroksymetylo-4-chloro-3-metylopirazolu 116 g (1,0 mol) 4-chloro-3-metylopirazolu w 50 ml metanolu rozpuszczono w 100 g (1,0 mol) 30%formaliny, w temperaturze pokojowej. Potem odparowano wodę i metanol. Tytułowy związek pozostał w postaci białej substancji stałej. Wydajność 95%.Preparation of N-hydroxymethyl-4-chloro-3-methylpyrazole 116 g (1.0 mol) of 4-chloro-3-methylpyrazole in 50 ml of methanol was dissolved in 100 g (1.0 mol) of 30% formalin at room temperature. Then water and methanol were evaporated. The title compound remained as a white solid. 95% yield.

Wytwarzanie diwodorofosforanu 3,4-dimetylopirazoliowego 96 g (1,0 mol) 3,4-dimetylopirazolu rozpuszczono w 115 g (1,0 mol) 85% kwasu fosforowego, w temperaturze pokojowej. Odparowano wodę zawartą w kwasie fosforowym. Otrzymany najpierw olej po kilku godzinach wykrystalizował dając tytułowy związek. Wydajność 98%.Preparation of 3,4-dimethylpyrazolium dihydrogen phosphate 96 g (1.0 mol) of 3,4-dimethylpyrazole were dissolved in 115 g (1.0 mol) of 85% phosphoric acid at room temperature. The water contained in the phosphoric acid was evaporated. The first oil obtained crystallized out after a few hours to give the title compound. 98% yield.

Wytwarzanie diwodorofosforanu 4-chloro-3-metylopirazoliowego 116 g (1,0 mol) 4-chloro-3-metylopirazolu rozpuszczono w 115 g (1,0 mol) 85% kwasu fosforowego, w temperaturze pokojowej. Odparowano wodę zawartą w kwasie fosforowym. Otrzymany najpierw olej po kilku godzinach wykrystalizował dając tytułowy związek. Wydajność 98%.Preparation of 4-Chloro-3-methylpyrazolium dihydrogenphosphate 116 g (1.0 mol) of 4-chloro-3-methylpyrazole was dissolved in 115 g (1.0 mol) of 85% phosphoric acid at room temperature. The water contained in the phosphoric acid was evaporated. The first oil obtained crystallized out after a few hours to give the title compound. 98% yield.

PL 195 428 B1PL 195 428 B1

Wytwarzanie nawozów zawierających inhibitor nitryfikacjiManufacture of fertilizers containing a nitrification inhibitor

Jako nawóz nośnikowy służyła mieszanina saletry amonowej i siarczanu amonowego (ASS). 2 g pirazolu rozpuszczono w małej ilości wody, ewentualnie (patrz tabela I) zadano stechiometryczną ilością kwasu fosforowego (1:1) i dodano 1 do 10 g polikwasu akrylowego albo polikwasu fosforowego. 2 kg nawozu nośnikowego w postaci granulatu ogrzano wstępnie do temperatury wynoszącej około 50°C i na talerzu obrotowym powoli spryskiwano mgławicowo mieszaniną zawierającą związek pirazolowy. W celu przyspieszenia schnięcia dosuszano gorącym powietrzem albo pod koniec spryskiwania, albo po przerwaniu spryskiwania.A mixture of ammonium nitrate and ammonium sulphate (ASS) was used as the carrier fertilizer. 2 g of pyrazole was dissolved in a little water, optionally (see Table I) was treated with a stoichiometric amount of phosphoric acid (1: 1) and 1 to 10 g of polyacrylic acid or polyphosphoric acid was added. 2 kg of a granular carrier fertilizer was preheated to a temperature of about 50 ° C and on a turntable slowly sprayed with a nebulizer mixture containing the pyrazole compound. In order to accelerate the drying, they were dried with hot air either at the end of spraying or after stopping spraying.

Badanie trwałości podczas składowaniaStability test during storage

Trwałość podczas składowania nawozów mineralnych oznaczano w teście szybkościowym. Badanie przeprowadzono z nawozem traktowanym związkami pirazolowymi będącymi inhibitorami według wynalazku oraz dla celów porównawczych z nawozem traktowanym związkami pirazolowymi różnymi od inhibitorów według wynalazku oraz z nawozem traktowanym dodatkowo polikwasami. W tym celu nawóz mineralny zawierający inhibitor nitryfikacji składowano w napowietrzanej suszarce przez 4 tygodnie w temperaturze wynoszącej 30°C, przy wilgotności względnej powietrza 40 do 50% i szybkości powietrza około 1,2 m/s. Stężenie inhibitora nitryfikacji na nawozie mineralnym oznaczano przed oraz po składowaniu i ubytek inhibitora nitryfikacji ustalano w procentach. Każdorazowo składowano około 10 do 30 g potraktowanego nawozu mineralnego. Przy tym stężenie związku pirazolowego jako inhibitora nitryfikacji na początku badania wynosiło 0,05 do 0,2% wagowego, w odniesieniu do traktowanego nawozu mineralnego. Ubytki otrzymane dla różnych związków pirazolowych podano w poniższej tabeli I.The storage stability of mineral fertilizers was determined in a speed test. The test was carried out with a fertilizer treated with the pyrazole compounds which are inhibitors according to the invention and for comparison purposes with a fertilizer treated with pyrazole compounds different from the inhibitors according to the invention and with a fertilizer additionally treated with polyacids. For this purpose, the mineral fertilizer containing the nitrification inhibitor was stored in an aerated dryer for 4 weeks at a temperature of 30 ° C, a relative air humidity of 40 to 50% and an air velocity of about 1.2 m / s. The concentration of the nitrification inhibitor on the mineral fertilizer was determined before and after the storage, and the loss of the nitrification inhibitor was determined as a percentage. About 10 to 30 g of the treated mineral fertilizer was stored each time. The concentration of the pyrazole compound as a nitrification inhibitor at the beginning of the test was 0.05 to 0.2% by weight, based on the treated mineral fertilizer. The losses obtained with the various pyrazole compounds are given in Table I below.

T ab el a IT ab el a I

Związek Relationship Ubytek w procentach Percentage loss 3-metylopirazol* 3-methylpyrazole * 100 100 3,4-dimetylopirazol* 3,4-dimethylpyrazole * 100 100 4-chloro-3-metylopirazol* 4-chloro-3-methylpyrazole * 100 100 fosforan 3-metylopirazolu* 3-methylpyrazole phosphate * 55 55 fosforan 3,4-dimetylopirazolu 3,4-dimethylpyrazole phosphate 31 31 fosforan 4-chloro-3-metylopirazolu 4-chloro-3-methylpyrazole phosphate 92 92 3,4-dimetylopirazol + polikwas akrylowy* 3,4-dimethylpyrazole + polyacrylic acid * 10 10 4-chloro-3-metylopirazol + polikwas akrylowy* 4-chloro-3-methylpyrazole + polyacrylic acid * 5 5 fosforan 3,4-dimetylopirazolu + polikwas akrylowy* 3,4-dimethylpyrazole phosphate + polyacrylic acid * 9 9 fosforan 4-chloro-3-metylopirazolu + polikwas akrylowy* 4-chloro-3-methylpyrazole phosphate + polyacrylic acid * 12 12 3,4-dimetylopirazol + polikwas fosforowy (1:20)* 3,4-dimethylpyrazole + polyphosphoric acid (1:20) * 0 0 3,4-dimetylopirazol + polikwas fosforowy (1:1)* 3,4-dimethylpyrazole + polyphosphoric acid (1: 1) * 12 12

* = doświadczenia porównawcze* = comparative experiments

Z wyników przedstawionych w tabeli I widać, że ubytek związku pirazolowego w potraktowanych inhibitorami nitryfikacji zgodnie z wynalazkiem nawozach mineralnych podczas składowania jest mniejszy niż w przypadku substancji porównawczych. Dodatkowe pokrycie nawozów polikwasem prowadzi do istotnie zmniejszonego ubytku inhibitora nitryfikacji.It can be seen from the results shown in Table I that the loss of pyrazole compound in the mineral fertilizers treated according to the invention during storage is lower than in the case of the reference substances. Additional coverage of fertilizers with polyacid leads to a significantly reduced loss of the nitrification inhibitor.

PL 195 428 B1PL 195 428 B1

Oznaczanie biologicznego działania inhibitorów nitryfikacjiDetermination of biological activity of nitrification inhibitors

Doświadczenia poloweField experiments

Biologiczną skuteczność 4-chloro-3-metylopirazolu (4Cl-3MP) oraz 3,4-dimetylopirazolu (3,4-DMP) w porównaniu z DCD i kontrolą badano w kilku doświadczeniach polowych w różnych środowiskach za pomocą parametrów, jak „zawartość azotanu w podstawie łodygi, „zawartość NO3- i NH4-N w glebie oraz „plon ziarna,The biological effectiveness of 4-chloro-3-methylpyrazole (4Cl-3MP) and 3,4-dimethylpyrazole (3,4-DMP) in comparison to DCD and control was tested in several field experiments in various environments using parameters such as "nitrate content in the base of the stem, "NO3- and NH4-N content in the soil and" grain yield,

Odnośnie plantacji, przeprowadzenia doświadczenia, zbioru i oceny doświadczeń polowych stosowano sposoby przyjęte w rolniczym doświadczalnictwie.The methods adopted in agricultural experimentation were used with regard to plantation, carrying out the experiment, harvesting and evaluation of field experiments.

Analizę prób roślin i gleby prowadzono metodami standardowymi. Pozostałe zabiegi produkcyjno-techniczne, jak ochrona roślin, odpowiadały dobrej praktyce rolniczej i przeprowadzano je jednolicie.The analysis of plant and soil samples was performed using standard methods. Other production and technical procedures, such as plant protection, corresponded to good agricultural practice and were carried out uniformly.

Biologicznie skuteczny inhibitor nitryfikacji odznacza się korzystnie tym, że w porównaniu z kontrolą (tu nawóz nośnikowy - mieszanina saletry amonowej i siarczanu amonowego - bez inhibitora nitryfikacji) po czasie wynoszącym do 8 tygodni od zastosowania w glebie, występują mniejsze zawartości NO3-N, a większe zawartości NH4-N (tabela 1). W następstwie tych warunków zostaje zmniejszone pobieranie azotanu przez rośliny (porównaj zawartość NO3 w podstawie łodygi roślin rzepaku, tabela 2) i często zostaje zwiększony plon ziarna (porównaj plon ziarna pszenicy ozimej, tabela 3a i 3b).A biologically effective nitrification inhibitor is advantageously characterized by the fact that, in comparison with the control (here a carrier fertilizer - a mixture of ammonium nitrate and ammonium sulphate - without a nitrification inhibitor), up to 8 weeks from the application in the soil, there are lower NO3-N content, and higher NH4-N content (Table 1). As a result of these conditions, the nitrate uptake by the plants is reduced (compare the NO3 content in the stem base of rapeseed plants, Table 2) and the grain yield is often increased (compare the grain yield of winter wheat, Table 3a and 3b).

Tabela 4 przedstawia opis stanowisk doświadczeń polowych.Table 4 shows the description of the field experiment sites.

Wyniki przedstawiono w poniższej tabeli 1. Wyraźnie widać, że wszystkie trzy inhibitory nitryfikacji wykazują dobrą skuteczność biologiczną w porównaniu z kontrolą. 4Cl-3MP i 3,4-DMP odznaczają się równie dobrą, a po części lepszą skutecznością w porównaniu z DCD, przy niewątpliwie znacznie mniejszych ilościach substancji czynnej.The results are shown in Table 1 below. It is clearly seen that all three nitrification inhibitors show good biological efficacy compared to the control. 4Cl-3MP and 3,4-DMP have equally good, and in part better, efficacy compared to DCD, with undoubtedly much smaller amounts of active ingredient.

Dalsze wyniki dla wybranych inhibitorów nitryfikacji przedstawiono w tabeli 5.Further results for selected nitrification inhibitors are presented in Table 5.

Użyty do badań porównawczych związek oznaczony skrótowo DCD oznacza dicyjanodiamid.The compound abbreviated DCD used in the comparative study is dicyandiamide.

T ab el a 1T ab el a 1

Oznaczanie biologicznego działania różnych inhibitorów nitryfikacji - Doświadczenia polowe Średnia zawartość NO3-i NH4-N w glebie (n = 5)Determination of biological activity of various nitrification inhibitors - Field trials Average NO3-and NH4-N content in soil (n = 5)

Tygodnie po zastosowaniu Weeks after application 2 2 4 4 6 6 8 8 Inhibitor nitryfikacji Nitrification inhibitor NO3-N kg/ha NO3-N kg / ha NH4-N kg/ha NH4-N kg / ha NO3-N kg/ha NO3-N kg / ha NH4-N kg/ha NH4-N kg / ha NO3-N kg/ha NO3-N kg / ha NH4-N kg/ha NH4-N kg / ha NO3-N kg/ha NO3-N kg / ha NH4-N kg/ha NH4-N kg / ha brak lack 82 82 97 97 75 75 49 49 61 61 50 50 43 43 20 twenty DCD DCD 47 47 87 87 44 44 68 68 35 35 82 82 29 29 39 39 4C1-3MP 4C1-3MP 61 61 115 115 50 50 79 79 39 39 76 76 28 28 40 40 3,4-DMP 3,4-DMP 54 54 82 82 43 43 70 70 44 44 71 71 28 28 37 37

Stanowiska: 1, 2, 3, 4i 5: opis - patrz tabela 4Positions: 1, 2, 3, 4 and 5: description - see table 4

PL 195 428 B1PL 195 428 B1

Tabel a 2Table a 2

Oznaczanie biologicznego działania różnych inhibitorów nitryfikacji - Doświadczenia polowe Średnia zawartość NO3 w podstawie łodyg roślin rzepaku (n = 5)Determination of the biological activity of various nitrification inhibitors - Field trials Average NO3 content in the stem base of oilseed rape plants (n = 5)

Tygodnie po zastosowaniu Weeks after application 2 2 4 4 6 6 8 8 Inhibitor nitryfikacji Nitrification inhibitor NO3 ppm NO3 ppm NO3 ppm NO3 ppm NO3 ppm NO3 ppm NO3 ppm NO3 ppm brak lack 8421 8421 7255 7255 5642 5642 5194 5194 DCD DCD 8036 8036 7022 7022 4728 4728 4274 4274 4C1-3MP 4C1-3MP 8112 8112 6629 6629 4774 4774 4276 4276 3,4-DMP 3,4-DMP 8105 8105 6720 6720 4899 4899 4454 4454

Stanowiska: 1, 2, 3, 4i 5: opis - patrz tabela 4Positions: 1, 2, 3, 4 and 5: description - see table 4

Tabel a 3aTable a 3a

Oznaczanie biologicznego działania różnych inhibitorów nitryfikacji - Doświadczenia polowe Pion ziarna pszenicy ozimejDetermination of biological activity of various nitrification inhibitors - Field experiments Winter wheat grain vertical

Inhibitor nitryfikacji Nitrification inhibitor Pion ziarna dt/ha Grain plummet dt / ha brak lack 52,8 52.8 DCD DCD 52, 6 52, 6 4Cl-3MP 4Cl-3MP 56,0 56.0

Stanowisko 4: opis - patrz tabela 4Station 4: description - see table 4

Tabel a 3bTable a 3b

Oznaczanie biologicznego działania różnych inhibitorów nitryfikacji - Doświadczenia polowe Pion ziarna pszenicy ozimejDetermination of biological activity of various nitrification inhibitors - Field experiments Winter wheat grain vertical

Inhibitor nitryfikacji Nitrification inhibitor Pion ziarna dt/ha Grain plummet dt / ha brak lack 95,4 95.4 DCD DCD 94,3 94.3 3,4-DMP 3,4-DMP 97,8 97.8

Stanowisko 2: opis - patrz tabela 4Station 2: description - see table 4

PL 195 428 B1PL 195 428 B1

Tabel a 4Table a 4

Oznaczanie biologicznego działania różnych inhibitorów nitryfikacji - Doświadczenia polowe Opis stanowiskDetermination of biological activity of various nitrification inhibitors - Field trials Job description

Stanowisko Position Temperatura roczna °C Annual temperature ° C Opad roczny mm Annual rainfall mm Typ gleby* Soil type * Punktowy wskaźnik bonitacji gleby uwzględniający warunki stanowiska Point soil valuation index taking into account the site conditions Wartość pH Value pH Zawartość próchnicy % Humus content% 1 1 8,8 8.8 600 600 L L. 68 68 7,3 7.3 1,3 1.3 2 2 7,8 7.8 817 817 tL tL 43 43 6,6 6.6 1,4 1.4 3 3 10,1 10.1 740 740 sL sL 45 45 6,5 6.5 1,2 1.2 4 4 9,9 9.9 550 550 IS IS 30 thirty 6,5 6.5 1,2 1.2 5 5 9,9 9.9 550 550 L L. 60 60 6,7 6.7 1,3 1.3

L: glinka lessowa sL: glina piaszczysta tL: glina gliniasta IS: piasek gliniastyL: loess loam sL: sandy loam tL: loam loam IS: loam sand

Tabel a 5Table a 5

Działanie różnych pirazoli hamujące nitryfikacjęNitrification inhibitory effects of various pyrazoles

Chemiczna nazwa Chemical name Działanie w tygodniach Action in weeks 1 1 2 2 4 4 6 6 8 8 3-metylopirazol (3-MP) 3-methylpyrazole (3-MP) 90 90 58 58 45 45 27 27 22 22 3,4-dirnetylopirazol (DMP) 3,4-dimethylpyrazole (DMP) 88 88 61 61 48 48 34 34 27 27 4Cl-3-metylopirazol (4Cl-3MP) 4Cl-3-methylpyrazole (4Cl-3MP) 88 88 66 66 48 48 32 32 21 21 Fosforan 4Cl-3-metylopirazolu 4Cl-3-methylpyrazole phosphate 91 91 62 62 53 53 45 45 27 27 N-hydroksy-4Cl-3MP N-hydroxy-4Cl-3MP 87 87 58 58 45 45 30 thirty 15 15 N-hydroksy-3,4-DMP N-hydroxy-3,4-DMP 85 85 54 54 40 40 31 31 10 10

*% hamowanie w stosunku do użytej ilości amonu*% inhibition with respect to the amount of ammonium used

Claims (3)

Zastrzeżenia patentowePatent claims 1. Nowe pochodne pirazolowe: N-hydroksymetylo-4-chloro-3-metylopirazol, N-hydroksymetylo3,4-dimetylopirazol, sól addycyjna 3,4-dimetylopirazolu z kwasem fosforowym, sól addycyjna 4-chloro3-metylopirazolu z kwasem fosforowym.1. New pyrazole derivatives: N-hydroxymethyl-4-chloro-3-methylpyrazole, N-hydroxymethyl-3,4-dimethylpyrazole, 3,4-dimethylpyrazole addition salt with phosphoric acid, 4-chloro-3-methylpyrazole addition salt with phosphoric acid. 2. Zastosowanie pochodnych pirazolowych: N-hydroksymetylo-4-chloro-3-metylopirazolu, N-hydroksy-metylo-3,4-dimetylopirazolu, soli addycyjnej 3,4-dimetylopirazolu z kwasem fosforowym, soli addycyjnej 4-chloro-3-metylopirazolu z kwasem fosforowym, chlorowodorku 3,4-dimetylopirazolu, jako inhibitorów nitryfikacji.2. Application of pyrazole derivatives: N-hydroxymethyl-4-chloro-3-methylpyrazole, N-hydroxymethyl-3,4-dimethylpyrazole, 3,4-dimethylpyrazole addition salt with phosphoric acid, 4-chloro-3-methylpyrazole addition salt with phosphoric acid, 3,4-dimethylpyrazole hydrochloride as nitrification inhibitors. 3. Nawóz mineralny zawierający azot i pochodne pirazolowe, znamienny tym, że zawiera w ilości 0,01 do 1,5% wagowych co najmniej jeden związek z pośród N-hydroksymetylo-4-chloro-3-metylopirazolu, N-hydroksymetylo-3,4-dimetylopirazolu, soli addycyjnej 3,4-dimetylopirazolu z kwasem fosforowym, soli addycyjnej 4-chloro-3-metylopirazolu z kwasem fosforowym, chlorowodorku 3,4-dimetylopirazolu.3. Mineral fertilizer containing nitrogen and pyrazole derivatives, characterized in that it contains in an amount of 0.01 to 1.5% by weight at least one compound of N-hydroxymethyl-4-chloro-3-methylpyrazole, N-hydroxymethyl-3 4-dimethylpyrazole, 3,4-dimethylpyrazole phosphoric acid addition salt, 4-chloro-3-methylpyrazole phosphoric acid addition salt, 3,4-dimethylpyrazole hydrochloride.
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